Sulfonated polymer and compositions thereof

ABSTRACT

This invention relates to unique and novel compositions based on chemically combining a sulfonated polymer and an amine terminated polylactone composition. The resulting amine neutralized sulfonated polymer compositions have a variety of uses including those as diverse as adhesive agents, thermoplastic elastomers, additive uses wherein these materials can be utilized to compatibilize two different polymers which are normally incompatible. These compositions can also be blended with fillers and/or oils when the sulfonated polymer is elastomeric. The materials display thermoplastic character.

This application is a continuation-in-part of U.S. Ser. No. 426,666filed Sept. 29, 1982 which is now U.S. Pat. No. 4,446,267 which in turnis a Rule 60 Division Ser. No. of 332,850 filed Dec. 21, 1981 which isnow U.S. Pat. No. 4,421,898.

FIELD OF THE INVENTION

This invention relates to unique and novel compositions based onchemically combining a sulfonated polymer and an amine terminatedpolylactone composition. The resulting amine neutralized sulfonatedpolymer compositions have a variety of uses including those as diverseas adhesive agents, thermoplastic elastomers, additive uses whereinthese materials can be utilized to compatibilize two different polymerswhich are normally incompatible. These compositions can also be blendedwith fillers and/or when the sulfonated polymer is elastomeric. Thematerials display thermoplastic character.

BACKGROUND OF THE INVENTION

Recently, a new class of thermoelastic sulfonated polymers has beendescribed in a number of U.S. patents. These sulfonated polymers arederived from polymeric materials having olefinic unsaturation,especially elastomeric polymers such as Butyl and EPDM rubbers. U.S.Pat. No. 3,642,728, herein incorporated by reference, clearly teaches amethod of selective sulfonation of olefinic unsaturation sites of anelastomeric polymer to form an acid form of a sulfonated elastomericpolymer. The olefinic sites of the elastomeric polymer are sulfonated bymeans of a complex of a sulfur trioxide donor and a Lewis base. The SO₃H groups of the sulfonated elastomer can be readily neutralized with abasic material to form an ionically cross-linked elastomer at roomtemperature. However, these ionically cross-linked elastomers may beprocessed like a conventional thermoplastic at elevated temperaturesunder a shear force in the presence of selected preferentialplasticizers, which dissipate the ionic association at the elevatedtemperatures, thereby creating a reprocessable elastomer.

The basic materials used as neutralizing agents are selected fromorganic amines or basic materials selected from Groups I, II, III, IV,V, VI-B and VIII, and mixtures thereof, of the Periodic Table ofElements.

U.S. Pat. No. 3,836,511, herein incorporated by reference, teaches animproved process for the sulfonation of the olefinic sites of theelastomeric polymer, wherein the improved sulfonating agent is selectedfrom acetyl sulfate, propionyl sulfate and butyryl sulfate. Theneutralizing agents employed to neutralize the acid form of thesulfonated elastomeric polymers are organic amines.

U.S. Pat. No. 3,870,841, herein incorporated by reference, teaches amethod of plasticization of the polymeric backbone of a neutralizedsulfonated plastic polymer by means of a polymer chain plasticizer whichis a liquid compound having a boiling point of at least about 120° C.The polymer chain plasticizer is selected from a dialkyl phthalate, aprocess oil or an organic acid ester. Additionally, a domain plasticizercan be incorporated into the composition, wherein the domain plasticizerreversibly disrupts the association of the sulfonated groups at atemperature of forming.

U.S. Pat. No. 3,847,854, herein incorporated by reference, teaches amethod of improving the processability of neutralized sulfonatedelastomeric polymers by the addition of a preferential plasticizer whichhas at least one functional constituent which exhibits a bond momentwhose absolute value is at least 0.6 Debyes, and must be a liquid at thedesired processing temperature of the neutralized sulfonated elastomericpolymer.

SUMMARY OF THE INVENTION

Sulfonated polymers have been shown to display many of thecharacteristics of a covalently cross-linked elastomer or plasticdespite the fact that these materials are only physically cross-linked.Such materials would be especially useful to employ in blendcompositions, with a variety of other polymers such as polyvinylchloride, polyurethanes, polystyrene, "Phenoxy A", polyethylene andsimilar compositions. However, sulfonated polymers are usuallyincompatible with such compositions except under unusual circumstances.

This invention is concerned with a new class of polymers based on thechemical combination of sulfonated polymers and an amine-terminatedpolylactone. As such, these polymers can have many of the physicalproperties of the base sulfonated polymer (such as Sulfo EPDM), but alsoderive many of the desirable features of the polylactone (such aspoly-ε-caprolactone). Generally, the sulfonated polymer and the lactonepolymer are not truly molecularly compatible and; therefore, are phaseseparated. Due to the fact that the sulfonated polymer is chemicallycombined with a novel class of amine terminated lactones, the resultinggrafted polymer system displays some properties of both polymer phases.

Since the polylactones, such as poly-ε-caprolactone, are widely knownfor their unique compatibility behavior, this invention permits thepreparation of polylactone neutralized sulfonated polymers which areuseful in a variety of polymer blends. In the case where Sulfo EPDM isthe base sulfonated polymer, the combination with amine-terminatedpoly-ε-caprolactone provides a "graft" system which can behave as atough and useful thermoplastic elastomer. Such compositions derive theirphysical properties, in part, from the ionic interactions, but mostlydue to the crystalline caprolactone domains which act as physicalcross-links. Such systems can also be modified through the addition ofoils and fillers, as in the case for other sulfonated elastomers. Theresulting materials can, under appropriate conditions, be meltprocessable.

This invention relates to unique and novel compositions based onchemically combining a sulfonated polymer and a tertiary amineterminated polylactone composition. The resulting amine neutralizedsulfonated polymer compositions have a variety of uses including thoseas diverse as adhesive agents, thermoplastic elastomers, additive useswherein these materials can be utilized to compatibilize two differentpolymers which are normally incompatible. These compositions can also beblended with fillers and/or oils when the sulfonated polymer iselastomeric. The materials display thermoplastic character.

The neutralized sulfonated elastomeric polymers of this presentinvention are derived from elastomeric of thermoplastic polymers whereinthe elastomeric polymers are derived from unsaturated polymers whichinclude low unsaturated elastomeric polymers such as Butyl rubbers orEPDM terpolymers.

Alternatively, other unsaturated polymers are selected from the groupconsisting of partially hydrogenated polyisoprenes, partiallyhydrogenated polyisoprenes, partially hydrogenated polybutadienes,Neoprene, styrene-butadiene copolymers or isoprenestyrene randomcopolymers.

The expression "Butyl rubber" as employed in the specification andclaims, is intended to include copolymers made from a polymerizationreaction mixture having therein from 70 to 99.5% by weight of anisoolefin which has about 4 to 7 carbon atoms, e.g., isobutylene andabout 0.5 to 30% by weight of a conjugated multiolefin having from about4 to 14 carbon atoms, e.g., isoprene. The resulting copolymer contains85 to 99.8% by weight of combined isoolefin and 0.2 to 15% of combinedmultiolefin.

Butyl rubber generally has a Staudinger molecular weight as measured byBPC of about 20,000 to about 500,000, preferably 25,000 to about 400,000especially about 100,000 to about 400,000 and a Wijs Iodine No. of about0.5 to 50, preferably 1 to 15. The preparation of Butyl rubber isdescribed in U.S. Pat. No. 2,356,128 which is incorporated herein byreference.

For the purposes of this invention, the Butyl rubber may haveincorporated therein from about 0.2 to 10% of combined multiolefin;preferably about 0.5 to about 6%; more preferably, about 1 to about 4%,e.g., 2%.

Illustrative of such a Butyl rubber is Exxon Butyl 365 (Exxon ChemicalCo.), having a mole perecent unsaturation of about 2.0% and a Mooneyviscosity (ML, 1+3, 212° F.) of about 40-50.

Low molecular weight Butyl rubbers, i.e., Butyl rubbers having aviscosity average molecular weight of about 5,000 to 85,000 and a molepercent unsaturation of about 1 to about 5% may be sulfonated to producethe polymer useful in this invention. Preferably, these polymers have aviscosity average molecular weight of about 25,000 to about 60,000.

The EPDM terpolymers are low unsaturated polymers having about 1 toabout 10.0 wt% olefinic unsaturation, more preferably about 2 to about8, most preferably about 3 to 7 defined according to the definition asfound in ASTM-D-1418-64 and is intended to mean terpolymers containingethylene and propylene in the backbone and a diene in the side chain.Illustrative methods for producing these terpolymers are found in U.S.Pat. No. 3,280,082, British Pat. No. 1,030,289 and French Pat. No.1,386,600, which are incorporated herein by reference. The preferredpolymers contain about 40 to about 75 wt% ethylene and about 1 to about10 wt% of a diene monomer, the balance of the polymer being propylene.Preferably, the polymer contains about 45 to about 70 wt% ethylene,e.g., 50 wt% and about 2.6 to about 8.0 wt% diene monomer, e.g., 5.0wt%. The diene monomer is preferably a nonconjugated diene.

Illustrative of these nonconjugated diene monomers which may be used inthe terpolymer (EPDM) are 1,4-hexadiene, dicyclopentadiene,5-ethylidene-2-norbornene, 5-methylene-2-norbornene,5-propenyl-2-norbornene, and methyl tetrahydroindene.

A typical EPDM is Vistalon 2504 (Exxon Chemical Co.), a terpolymerhaving a Mooney viscosity (ML, 1+8, 212° F.) of about 40 and having anethylene content of about 50 wt% and a 5-ethylidene-2-norbornene contentof about 5.0 wt%. The Mn as measured by GPC of Vistalon 2504 is about47,000, the Mv as measured by GPC is about 145,000 and the Mw asmeasured by GPC is about 174,000.

Another EPDM terpolymer Vistalon 2504-20 is derived from Vistalon 2504(Exxon Chemical Co.) by a controlled extrusion process, wherein theresultant Mooney viscosity at 212° F. is about 20. The Mn as measured byGPC of Vistalon 2504-20 is about 26,000, the Mv as measured by GPC isabout 90,000 and the Mw as measured by GPC is about 125,000.

Nordel 1320 (DuPont) is another terpolymer having a Mooney viscosity at212° F. of about 25 and having about 53 wt% of ethylene, about 2.5 wt.%of 1,4-hexadiene, and about 43.5 wt% of propylene.

The EPDM terpolymers of this invention have a number average molecularweight (Mn) as measured by GPC of about 10,000 to about 200,000, morepreferably about 15,000 to about 100,000, most preferably of about20,000 to about 60,000. The Mooney viscosity (ML, 1+8, 212° F.) of theEPDM terpolymer is about 5 to about 60, more preferably about 10 toabout 50, most preferably about 15 to about 40. The Mv as measured byGPC of the EPDM terpolymer is preferably below about 350,000 and morepreferably below about 300,000. The Mw as measured by GPC of the EPDMterpolymer is preferably below about 500,000 and more preferably belowabout 350,000.

The neutralized sulfonated thermoplastic polymers of the instantinvention are derived from polystyrene type thermoplastics polymerswhich are selected from the group consisting of polystyrene,poly-t-butyl-styrene, polychlorostyrene, polyalpha methyl styrene andco- or terpolymers of the aforementioned with acrylonitrile or vinyltoluene.

The polystyrene thermoplastics suitable for use in the practice of theinvention have a glass transition temperature from about 90° C. to about150° C., more preferably about 90° C. to about 140° C. and mostpreferably about 90° C. to about 120° C. These polystyrene resins have aweight average molecular weight as measured by GPC of about 5,000 toabout 500,000 more preferably about 20,000 to about 350,000 and mostpreferably 90,000 to about 300,000. These base polystyrene thermoplasticresins can be prepared directly by any of the known polymerizationprocesses. The term "Thermoplastic" is used in its conventional sense tomean a substantially rigid (flexus modulus 10,000 psi) material capableof retaining the ability to flow at elevated temperatures for relativelylong times.

The preferred polystyrene thermoplastic resin is a homopolymer ofstyrene having a number average molecular weight of about 180,000, andan intrinsic viscosity in toluene of about 0.8. These polymers arewidely available commercially in large volume. A suitable material isStyron 666 which affords a number molecular weight of about 105,000.

In carrying out the invention, the polymer is dissolved in a nonreactivesolvent such as a chlorinated aliphatic solvent, chlorinated aromatichydrocarbon, an aromatic hydrocarbon, or an aliphatic hydrocarbon suchas carbon tetrachloride, dichloroethane, chlorobenzene, benzene,toluene, xylene, cyclohexane, pentane, isopentane, hexane, isohexane, orheptane. The preferred solvents are the lower boiling aliphatichydrocarbons. A sulfonating agent is added to the solution of theelastomeric polymer and nonreactive solvent at a temperature of about-100° C. to about 100° C. for a period of time of about 1 to about 60minutes, most preferably at room temperature for about 5 to about 45minutes; and most preferably about 15 to about 30. Typical sulfonatingagents are described in U.S. Pat. Nos. 3,642,728 and 3,836,511,previously incorporated herein by reference. These sulfonating agentsare selected from an acyl sulfate, a mixture of sulfuric trioxide donorand a Lewis base containing oxygen, sulfur, or phosphorous. Typicalsulfur trioxide donors are SO₃, chlorosulfonic acid, fluorosulfonicacid, sulfuric acid, oleum, etc. Typical Lewis based are: dioxane,tetrahydrofuran, tetrahydrothiophene or triethyl phosphate. The mostpreferred sulfonation agent for this invention is an acyl sulfateselected from the group consisting essentially of benzoyl, acetyl,propionyl or butyryl sulfate. The acyl sulfate can be formed in situ inthe reaction medium or pregenerated before its addition to the reactionmedium in a chlorinated aliphatic or aromatic hydrocarbon.

It should be pointed out that neither the sulfonating agent nor themanner of sulfonation is critical, provided that the sulfonating methoddoes not degrade the polymer backbone. The reaction is quenched with analiphatic alcohol such as methanol, ethanol or isopropanol, with anaromatic hydroxyl compound, such as phenol, a cycloaliphatic alcoholsuch as cyclohexanol or with water. The unneutralized sulfonatedelastomeric polymer has about 10 to about 200 meq unneutralizedsulfonate groups per 100 grams of sulfonated polymer, more preferablyabout 15 to about 100; and most preferably about 20 to about 80. The meqof unneutralized sulfonate groups per 100 grams of polymer is determinedby both titration of the polymeric sulfonic acid and dietert Sulfuranalysis. In the titration of the sulfonic acid, the polymer isdissolved in solvent consisting of 95 parts of toluene and 5 parts ofmethanol at a concentration level of 50 grams per liter of solvent. Theunneutralized form is titrated with ethanolic sodium hydroxide to anAlizarin-Thymolphthalein endpoint.

The unneutralized sulfonate polymer is gel free and hydrolyticallystable. Gel is measured by stirring a given weight of polymer in asolvent comprised of 95 toluene-5-methanol at a concentration of 5 wt%,for 24 hours, allowing the mixture to settle, withdrawing a weighedsample of the supernatant solution and evaporating to dryness.

Hydrolytically stable means that the acid function, in this case thesulfonic acid, will not be eliminated under neutral or slightly basicconditions to a neutral moiety which is incapable of being converted tohighly ionic functionality.

Neutralization of the unneutralized sulfonated polymer is done by theaddition of a solution of a polycaprolactone polymer to theunneutralized sulfonated elastomeric polymer typically dissolved in themixture of the aliphatic alcohol and nonreactive solvent. Thepolycaprolactone polymer is dissolved in a solvent system consisting oftoluene, optionally containing an aliphatic alcohol. Thesepolycaprolactone polymers are formed by the reaction of ε-caprolactonewith an organic diamine in the presence of a catalyst as described in acopending application. The anhydrous ε-caprolactone and the organicdiamine in the presence of the catalyst are reacted together in areaction vessel in the absence of a solvent at a temperature of about50° to about 200° C., more preferably about 75° to about 180° and mostpreferably about 90° to about 100° C. for a sufficient period of time toeffect polymerization.

The reaction of the ε-caprolactone with the diamine which has oneprimary or secondary amine group and at least one amine group which iscontained in a cyclic, heterocyclic, unsaturated or aromatic ringstructure can be generally depicted by the equation: ##STR1## whereinn=1 to 500 and m=0 to 20

Typical, but non-limiting examples of other useful aromatic orheterocyclic organic amines are: ##STR2## where m is 0 to 20

Catalysts useful in the promotion of the above identified reaction areselected from the group consisting of stannous octanoate stannoushexanoate, stannous oxalate, tetrabutyl titanate, a variety of metalorganic based catalysts, acid catalysts and amine catalysts, asdescribed on page 266, and forwarded in a book chapter authored by R. D.Lundberg and E. F. Cox, entitled Kinetics and Mechanisms ofPolymerization: Ring Opening Polymerization; edited by Frisch and Rugen,published by Marcell Dekker in 1969, wherein stannous octanoate is anespecially preferred catalyst. The catalyst is added to the reactionmixture at a concentration level of about 100 to about 10,000 parts ofcatalyst per 1 million parts of ε-caprolactone.

The resultant polycaprolactone polymer has an Mn as measured by GPC ofabout 200 to about 50,000 more preferably about 500 to about 40,000, andmost preferably about 700 to about 30,000 and a melting point from belowroom temperature to about 55° C., more preferably about 20° C. to about52° C., and most preferably about 20° C. to about 50° C.

The metal sulfonate-containing polymers at the higher sulfonate levelspossess extremely high melt viscosities and are thereby difficult toprocess. The addition of ionic group plasticizers markedly reduces meltviscosity and frequently enhances physical properties.

To the neutralized sulfonated polymer is added, in either solution or tothe crumb of the unneutralized form of the sulfonated polymer, apreferential plasticizer selected from the group consisting ofcarboxylic acids having about 5 to about 30 carbon atoms, morepreferably about 8 to about 22 carbon atoms, or basic salts of thesecarboxylic acids, wherein the metal ion of the basic salt is selectedfrom the group consisting of aluminum, ammonium, lead or Groups I-A,II-A, I-B and II-B of the Periodic Table of Elements, and mixturesthereof. The carboxylic acids are selected from the group consisting oflauric, myristic, palmitic or stearic acids and mixtures thereof; e.g.,zinc stearate, magnesium stearate, or zinc laurate.

The preferential plasticizer is incorporated into the neutralizedsulfonated polymer at less than about 60 parts by weight per 100 partsof the sulfonated polymer more preferably at about 5 to about 40, andmost preferably at about 7 to about 25. Alternatively, otherpreferential plasticizers are selected from ureas, thioureas, amines,amides, ammonium and amine salts of carboxylic acids and mixturesthereof. The preferred plasticizers are selected from fatty acid ormetallic salts of fatty acid and mixtures thereof. The resultantneutralized sulfonated polymer with preferential plasticizer is isolatedfrom the solution by conventional steam stripping and filtration.

Various other additives can be incorporated into the blend compositionsto improve the physical properties, the appearance, the chemicalproperties of the formed elastomeric article or to modify theprocessability of the blend compositions.

A crystalline polyolefinic thermoplastic can be incorporated into theblend composition in minor proportions as a means for modification ofthe rheological properties of the blend compositions as well as thestiffness of the elastomeric article. Typically, the crystallinepolyolefinic thermoplastic is added to the blend composition at aconcentration level of less than about 100 parts by weight per 100 partsof sulfonated polymer, more preferably at about 0 to about 75; and mostpreferably at about 0 to about 50.

The crystalline polyolefin is characterized as a polymer of analphaolefin having a molecular weight of at least 2,000 preferably atleast 10,000, and more preferably at least 20,000. This materialcomprises substantially an olefin but may incorporate other monomers,for example, vinyl acetate, acrylic acid, methyl acrylate, ethylacrylate, sodium acrylate, methyl methacrylate, ethyl methacrylate,methacrylic acid, sodium methacrylate, etc. The preferred polyolefinsare selected from the group consisting of polymers of C₂ to C₄alphaolefins. Most preferably the polyolefins are selected from thegroup consisting of polyethylene, polybutene, polypropylene, andethylene-propylene copolymers. It is critical that the crystallinepolyolefin have a high degree of crystallinity of at least 25% and mostpreferably at least 40%.

Both high and low density polyethylene are within the scope of theinstant invention. For example, polyethylenes having a density from 0.90to 0.97 gms/cc. are generally included. Polypropylene polymers havingintermediate and high densities are the preferred examples of thepolypropylene materials useful in the instant invention. These materialswill have a density from 0.88 to 0.925 gms/cc. The polyethylene orpolypropylene can also be combined as copolymers thereof so long asadequate crystallinity is obtained in said combination. Thus, blockcopolymers wherein polyethylene or polypropylene is present incrystalline form are effective.

Zinc oxide can be incorporated into the blend as a whitening pigment aswell as a means for improving the ionic bonding force between thesulfonate groups in the sulfonated elastomeric polymer. The zinc oxideis incorporated into the blend composition at a concentration level ofless than about 0 to about 25 parts by weight per 100 parts ofsulfonated polymer, more preferably about 5 to about 15. Alternatively,a Rutile or Anatese titanium dioxide can be employed as a whiteningpigment.

A lubricant can be employed in the blend composition at a concentrationlevel of less than about 20 parts by weight per 100 parts of theneutralized sulfonated polymers, and more preferably about 1 to about15. The lubricants of the present instant invention are nonpolarparaffinic hydrocarbon waxes having a softening point of about 135° F.to about 220° F., more preferably 150° F. to 200° F., wherein the waxhas a number average molecular weight of about 1000 to about 4000, morepreferably 1500 to 3500, and less than about 2 wt% polar constituents.These lubricants modify the rheological properties of the composition,improve the processability in forming the elastomeric article and imparta shine or gloss to the elastomeric article. Additionally, amorphouspolypropylene can be used as a lubricant.

The ingredients incorporated into the blend compositions of the presentinvention, in conjunction with the type of elastomeric polymer, thedegree of sulfonation, and the metal counterion of the neutralizedsulfonated polymer and the plasticizer give materials processably byextrusion or injection molding processes into elastomeric articleshaving the desirable physical and rheological properties. These combinedphysical properties and rheological processability characteristics werenot previously obtainable in the aforementioned U.S. patents andapplications previously incorporated herein by reference.

The polymer compositions prepared according to this invention cover avariety of new systems and applications. For example, Sulfo EPDMneutralized with tertiary amine terminated poly-ε-caprolactone canpossess a variety of properties depending on sulfonic acid content andpoly-ε-caprolactone (or PCL) molecular weight. Thus, a high molecularweight PCL (for example, a number average molecular weight of 10,000)coupled with Sulfo EPDM of 30 milliequivalents per 100 grams sulfonicacid content would require about 300 grams of PCL per 100 grams of SulfoEPDM to effect neutralization. Such a composition, therefore, would beabout 75 percent PCL. On the other hand, the use of a PCL polymer of1,000 molecular weight would result in a neutralized graft ionomer ofabout 23 percent PCL. The physical properties of these two compositionswill obviously vary substantially, depending on the compositions.

Similarly, sulfonated polystyrene (S-PS) can be neutralized with PCL. Inthis case, polystyrene can be sulfonated over a range of sulfonic acidcontents from as little as 1 mole percent up to about 100 mole percent.In the former case, only 1 of every 100 repeat units contains sulfonicacid groups, while in the latter case, every aromatic group issulfonated. Obviously, the range of compositions available, depending onthe PCL molecular weight of the sulfonic acid content, is extremelylarge. The variation in physical properties available, similarly, islarge.

The application to which these novel polymers can be put to use isvaried. The PCL/Sulfo EPDM grafts are useful as thermoplastic elastomersand potential adhesives.

Other types of polymer sulfonic acids suitable in this invention includesulfonated polybutadiene, sulfonated polyisoprene, sulfonated Butyl,sulfonated SBR, sulfonated polypentenomer, etc. Of special interest arepolymers with terminal unsaturation such as polyisobutylene. Typically,this polymer is terminated with an olefin group which can be sulfonatedto provide a long chain polyisobutylene of from 500 to 25,000 inmolecular weight. Sulfonation of this functionality provides a polymerwith a sulfonic acid group at just one end, and which can then beneutralized to provide a polyisobutylene/PCL block copolymer composed ofjust two blocks.

The sulfonated aromatic polymers can be of special use as potentialcompatibilizers or adhesives between polymers which do not normallyadhere or blend to form compatible blends. Examples of such polymers areButyl rubber and polyvinyl chloride or polyisobutylene andpolyester-based polyurethanes.

The potential list of polymers which can be adhered or blended togetherby the use of these concepts is extensive and will be summarized onlybriefly in this application. Obviously, the list of polymers suitablefor such uses will depend on the particular PCL/Sulfonated polymerconsidered. The following list is intended to represent combined systemsfor several types of such grafts, as indicated.

                  TABLE I                                                         ______________________________________                                        COMPATIBILITY TABLE FOR SULFO                                                 POLYSTYRENE/PCL GRAFTS                                                        Column A          Column B                                                    Polymer Phase Compatible                                                                        Polymer Phase Compatible                                    with Polystyrene  with PCL                                                    ______________________________________                                        Polystyrene       Polyvinyl chloride                                          Rubber toughened  Nitrocellulose                                              polystyrene       Low density polyethylere                                    (impact modified)                                                             Acrylonitrile/butadiene/                                                                        Phenoxy A                                                   styrene                                                                       Terpolymer (ABS resin)                                                                          Polyvinyl butyral                                           Styrene/acrylonitrile                                                                           Polyester based                                             copolymers        polyurethanes                                               Styrene/methyl-   Vinyl chloride/vinylidene                                   methacrylate      chloride copolymers                                         copolymers                                                                    ______________________________________                                    

While this is only a partial list of systems, it is intended to show theversatility of the polymer grafts described in this invention.

Unless otherwise specified, all measurements are in parts by weight per100 parts of sulfonated polymer.

EXAMPLE 1

A sample of diamine initiated polyε-caprolactone was prepared asfollows: 97.1 ml of distilled ε-caprolactone was placed in a reactionvessel and to the lactone was added 42.1 grams of N-amino propylmorpholine (NAPM) and 0.25 ml stannous octoate. This combination ofdiamine initiator and lactone were designed to give a polymer of about500 molecular weight. The reactants were stirred and heated for about 2hours while gradually raising the temperature to 150° C. Thepolymerization reaction was continued at 150°-153° C. for an additional1 hour and 20 minutes. It was noted that the clear solution changedcolor to orange and then to reddish black and the reaction mixturebecame thicker. The reaction mixture was poured into a Teflon coatedaluminum container and cooled obtaining a thick dark liquor. Theanalytical data for this sample are shown in Table I.

EXAMPLE 2

In a similar manner to Example 1, a polyε-caprolactone with a molecularweight of 2000 was prepared by reacting 97.1 ml distilledε-caprolactone, 7.9 g N-amino propyl morpholine (NAPM) and 0.25 mlstannous octoate. Reaction temperature was raised to 150° C. over aperiod of about 2 hours and held at 150°-154° C. for 1 and 1/2 hours. Achange in color to dark red-blue was noted. The reaction mixture becamevery thick. Cooling of the reaction mixture produced a hard brown waxysolid. Analytical data are shown in Table I.

EXAMPLE 3

Using the procedure of Example 1, a polyε-caprolactone of molecularweight 4000 was prepared by reacting under similar conditions, 97.1 mldistilled ε-caprolactone, 3.73 g N-amino morpholine (NAPM) and 0.25 gstannous octoate. Color developed to yellow-orange and the reactionmixture thickened. Cooling after the same reaction period produced ahard white waxy solid. Analytical data are shown in Table I.

EXAMPLE 4

Using the same procedure of Example 1, a polyε-caprolactone of molecularweight 8000 was prepared by reacting under similar conditions, 97.1 mlε-caprolactone, 1.88 g N-amino propyl morpholine (NAPM) and 0.25 gstannous octoate. A yellow orange color and thickening of the reactionmixture was noted. After the same reaction period, the mixture wascooled producing a hard white wax solid. Analytical data are shown inTable II.

                  TABLE II                                                        ______________________________________                                        NITROGEN ANALYZERS AND REDUCED                                                VISCOSITY CHARACTERIZATION OF POLYMER                                         SAMPLES: (XYLENE)                                                                                           Reduced                                                   Target              Viscosity of                                              Molecular           2% Solution                                     Sample    Weight       % N    Xylene, 25° C.                           ______________________________________                                        Example 1   500        5.45   Not Completely                                                                Soluble                                         Example 2 2,000        1.33   0.096                                           Example 3 4,000        0.70   0.185                                           Example 4 8,000        0.33   0.305                                           ______________________________________                                    

These experiments clearly demonstrate that a polymer of ε-caprolactonecan be obtained employing the NAPM initiator. Furthermore, the molecularweight obtained with this initiator increases as the amount of initiatoris decreased as shown by the reduced viscosity measurements of Table Iand also as supported by the nitrogen analysis results in Table I. Theseexperiments clearly demonstrate how this family of initiators can beemployed to control polymer molecular weight to any desired degree.

Neutralization of Sulfo-Polystyrene Acid with Polyε-Caprolactone-N-AminoPropyl Morpholines.

A sulfonated polystyrene containing 3.37 mole % sulfonic acid wasneutralized using the polyε-caprolactone-N-Amino propyl morpholineadducts prepared in Examples 1-4 as described in the following examples.

EXAMPLE 5

In a 500 ml reaction vessel, 25 g of 3.37 mol % sulfo-polystyrene acidwas dissolved in 250 ml of dichloroethane. A solution of 4.22 gpoly-ε-caprolactone-N-Amino propyl morpholine, 500 molecular weight(Example 1) in 25 ml dichloroethane was added and the reactants stirredat ambient temperature for four hours. The product was recovered byprecipitating and washing with excess hexane, air drying in a hood andfinally vacuum oven drying at 60° C. for one day.

EXAMPLE 6

In a 500 ml reaction vessel charged 25 g of 3.37 mol % sulfopolystyrene,16.85 g poly-ε-caprolactone-N-amino propyl morpholine, 2000 molecularweight (Example 2) and 275 ml dichloroethane. The reactants were stirredat ambient temperature to dissolve and stirring continued for fourhours. Product was recovered as described in Example 5.

EXAMPLE 7

In a 500 ml reaction vessel charged 15 g of 3.37 mol% sulfopolystyrene,20.22 g poly-ε-caprolactone-N-amino propyl morpholine, 4000 molecularweight (Example 3) and 250 ml dichloroethane. The reactants were stirredat ambient temperature to dissolve and stirring continued for 4 hours.Product was recovered as described in Example 5.

EXAMPLE 8

In a 500 ml reaction vessel charged 10 g of 3.37 mol% sulfopolystyrene,26.96 g poly-ε-caprolactone-N-amino propyl morpholine, 8000 molecularweight (Example 4) and 250 ml dichloroethane. The reactants were stirredat ambient temperature to dissolve and stirring continued for 4 hours.Product was recovered as described in Example 5.

                  TABLE III                                                       ______________________________________                                        Nitrogen analysis and reduced viscosity vs.                                   concentration in xylene of sulfo-polystyrene-poly-ε-                  caprolactone-N--amino propyl morpholine of Examples                           5-8.                                                                                   Reduced Viscosity At 25° C.                                                  5%      2%     1%    0.5%   0.25%                              Sample  % N    Conc.   Conc.  Conc. Conc.  Conc.                              ______________________________________                                        Example 5                                                                             0.77   --      (Polymer precipitated upon dilution)                   Example 6                                                                             0.54   1.90    0.763  0.566 0.473  0.417                              Example 7                                                                             2.37   2.23    0.961  0.714 0.591  0.512                              Example 8                                                                             0.31   2.78    1.22   0.891 0.702  0.597                              ______________________________________                                    

                  TABLE IV                                                        ______________________________________                                        Viscosity vs. temperature of 5% concentra-                                    tion solutions of sulfo-polystyrene-poly-ε-caprol-                    actone-N--amino propyl morpholines of Examples 5-8.                                  Brook Field Viscosity, Cp at                                           Sample   0° C.                                                                          25° C.                                                                          50° C.                                                                        75° C.                                                                        100° C.                        ______________________________________                                        Example 5                                                                              (Geis   23.6     9.9    4.91   3.14                                           Out)                                                                 Example 6                                                                              11.8    6.34     4.25   3.20   2.50                                  Example 7                                                                              12.2    7.25     5.07   3.85   3.05                                  Example 8                                                                              11.4    8.94     6.19   4.63   3.55                                  ______________________________________                                    

What is claimed is:
 1. A sulfonated polymer which has about 10 to about200 meq. of sulfonate groups per 100 grams of said sulfonated polymer,said sulfonate groups being neutralized with a polycaprolactone polymer,said polycaprolactrone polymer having an Mn measured by GPC of about 200to 50,000, said polycaprolactone polymer having the formula selectedfrom the groups consisting of a polycaprolactone formed by the reactionof an ε-caprolactone with an amine compound having the formula selectedfrom the group consisting of: ##STR3## wherein R₁, R₂, and R₃ areselected from the group consisting of hydrogen, alkyl groups havingabout 1 to about 10 carbon atoms and aryl groups having about 1 to about10 carbon atoms, x is an integer of from 4 to 7 and m is an integer offrom 0 to 20 said sulfonated polymer being formed from a polymerselected from the group consisting of EPDM terpolymer, Butyl rubber,polystyrene, poly-t-butyl styrene, polychlorostyrene and polymethylstyrene.
 2. A polymer according to claim 1 wherein R₁ and R₂ are analkyl group and R₃ is hydrogen.
 3. A polymer according to claim 1wherein either R₁ or R₂ is a methyl group and R₃ is hydrogen.
 4. Apolymer according to claim 1, wherein R₁ and R₂ are both methyl groupsand R₃ is hydrogen.
 5. A polymer according to claim 1, wherein R₁, R₂,and R₃ are methyl groups.
 6. A polymer according to claim 1 wherein saidEPDM terpolymer consists essentially of about 40 to 75 wt% of ethyleneof about 10 to about 53 wt% of propylene and of about 2 to about 20 wt%of a nonconjugated diene.
 7. A polymer according to claim 6, whereinsaid nonconjugated diene is selected from the group consisting of1,4-hexadiene, dicyclopentradiene, 5-alkylidene-2-norbornenes,5-alkenyl-2-norbornenes and tetrahydroindene.
 8. A polymer according toclaim 7, wherein said nonconjugated diene is 5-ethylidene-2-norbornene.9. A polymer according to claim 1, further including about 25 to about150 parts by weight of a nonpolar process oil per 100 parts of thesulfonated polymer, about 50 to about 300 parts by weight of a fillerper 100 parts of the sulfonated polymer.
 10. A composition according toclaim 9, further including a preferential plasticizer having a meltingpoint of at least 25° C. and said plasticizer is selected from the groupconsisting of carboxylic acids having at about 8 to about 22 carbonatoms, metallic salts of said carboxylic acids, urea, thioureas, amides,ammonium and amine salts of said carboxylic acids and amines andmixtures thereof, said composition containing about 5 to about 40 partsby weight of the plasticizer per 100 parts of said sulfonated polymer.11. A composition according to claim 9, wherein said preferentialplasticizer is a combination of a carboxylic acid and a metallic salt ofsaid carboxylic acid, a metal ion of said metallic salt being selectedfrom the group consisting of aluminum, antimony, iron, lead and GroupsI-A, II-A, I-B and II-B of the Periodic Table of Elements and mixturesthereof.
 12. A composition according to claim 9 wherein said filler isselected from the group consisting of clay, talc and calcium carbonate,and mixtures thereof.
 13. A composition according to claim 9, whereinsaid nonpolar process oil is selected from the group consisting ofparaffinic, naphthenic and aromatics and mixtures thereof.